Trifluoroalkoxyalkyl substituted organosilicon compounds



' silanes having the formula:

United States Patent ()fiice 3,132,117 Patented May 5, 1964TRIFLUOROALKOXYALKYL SUBSTITUTED ORGANOSILICON COMPOUNDS Gustav A.Schmidt, Schenectady, N.Y., assignor to gens-a1 Electric Company, acorporation of New or No Drawing. Filed Oct. 31, 1960, Ser. No. 65,926 7Claims. (Cl. 260-465) 3 )2- )2* ')a a a and substitutedcyclopolysiloxanes that have the formula:

L SiO II?" i Llii/ iu Where R is a member selected from the class ofhydrogen and lower alkyl groups, R is a member selected from the classof monovalent hydrocarbonradicals and halogenated monovalent hydrocarbonradicals, X is halo, a is an integer equal to from 0 to 2, inclusive, [2is an integer equal to from 1 to 10, inclusive, c is a whole numberequal to from 0 to 9, inclusive, and the sum of b and c is equal to from3 to 10, inclusive.

Included within the scope of the radicals represented by R of Formulae 1and 2 are hydrogen and lower alkyl radicals such as methyhethyl,pr0pyl,butyl, etc. radicals. Radicals that are included in R of Formulae1 and 2 are 'aryl radicals and halogenated aryl radicals such asnaphthyl, tolyl, phenyl, halophenyl, etc. radicals; aralkyl radicalsincluding benzyl, phenylethyl, etc. radicals; aliphatic andcycloaliphatic radicals, including alkenyl," such as vinyl, propenyl,etc. radicals; alkyl such as methyl, ethyl, propyl, butyl,etc.'radicals; cyclohexyl, etc. radicals; haloalipha'tic includingchloroalkyl, such as chloropropyl, etc.

radicals. R and R'can be all -the samefradical or a mixture 'of any twoor more of the aforementioned radicals respectively, R is preferablyydrogenand R'jis prefer I ably methyl, phenyl and halophenyl. l 1

' The novel tri-fluoroalkoxyalkyl substituted organosilicon compounds ofFormulae 1 and 2 can be homopolymerized or 'copolymerized withconventional organohalosilanes or cyclopolysiloxanes in accordance withart recognized cohydrolysis and equilibration procedures, resulting inmo lefil'lar rearrangement and intercondensation of organosiloxy unitsto produce a variety of useful trifluoroalkoxyalkyl substitutedorganopolysiloxanes in the'form of fluids, resins, and rubbers. IRepresentative of the organosilicon compounds that can. a

be intercondensed with the tr-ifluoroalkoxyalkyl I silicon ,R d i-d' andcyclopolysiloxanes to produce the trifluoroalkoxyalkyl substitutedorganopolysiloxanes of the present invention.

4 where R and X are as defined above, and R includes monovalent andhalogenated monovalent hydrocarbon radicals within the scope of R asdefined above, and cyanoalkyl radicals, preferably cyanoethyl radicals,d is an integer equal to from 1 to 3, inclusive, e is an integer equalto from 3 to 10, inclusive, f is equal to from .01 to 2, inclusive, g isequal to from 0.99 to 2, inclusive, the sum of f and g is equal to from1 to 3, inclusive.

The novel trifluoroalkoxyalkyl substituted organosilicon compounds ofFormulael and 2,can be made by the addition of a trifluoroalkoxyalkenehaving theformula:

l a )2 )2 to What will be referred to as a silicon hydride which can bea silane having the formula:

or a cyclopolysiloxane having the formula:

tions. For example, substituted organopolysiloxanes of Formula 5 thathave a ratio of 1.95 to 2.01 organic radicals, includingtrifiuoroalkoxyalkyl radicals, per silicon atom attached to silicon bycarbon-silicon linkages that areconvertible to the cured, solid, elasticstate and contain 5 to 95, and preferably 5 to 30 mol percent oftrifl-uoroalkoxyalkyl radicals based on the total nurirber oforganicradic-als in said or'ganopolysiloxanes can be reinforced withconventional fillers such as silica fillers, and semi reinforcingfillers including lead oxide, calcium carbonate, etc. to produceorganopolysiloxane elastomers having improved, oil resistance. Theorganopolysiloxanes of Formula Shaving a ratio of 2.01 to 3.0 organicradicals per silicon atom attachedto silicon by carbon-silicon linkages,includingtrifluoroalkoxyalkyl radicals in the range of 5 to mol percent,and preferably 5 to 50 mol percent based on the total number of organicradicals in said organopolys-iloxane can be employed as plasticizers forsynto form the trifluoroalkoxyal kyl substituted onganosilicon compoundsofthe present invention. The compounds compounds ofFormulae v1 and 2 aQVe are organ9haloof Ihe'presen't unvemwn can theube' mteroondensed' m amixture the aforesaid trifluoro compoundand silicon. hydride in thepresence of afinely divided metal catalyst such as platinumonlearbomchloroplatinic, etc 3, In form:

' 020 parts, of the 1,1,1 H

chlorosilane of Example "1 was placed into a reactionj stirred rfor anadditional 3 ing the trifluoroalkoxyalkeneasilicon hydride mixture, ithas been [found expedient to add the silicon hydride to a mixture of thetrilluoroalkoxyalkene and the metal catalyst, particularly when thesilicon hydride is a halo-' silane. The ratio of reactants employedduring the addition reaction is not critical and is largely dictated byeconomicconsider ation, lt is preferred to employ thetrifluoroalkoxyalkme :and'the silicon hydride stoiohimetric proportions.The finely divided metal catalyst can be employed in concentrationsranging from 0.0005 parts to 0.1 parts per part of the reaction mixture.

Temperatures in the range of 30 C. to 150 C. can be employed during theaddition reaction. The addition reaction can vary over a period of froman hour or less to many hours, depending on the rate of addition,catalyst employed, etc.

The trifluoroalk oxyalky-l substituted organosilicon com pounds of thepresent invention can then be cohydrolyzied or inter-condensed inaccordance with well known pro cedures either alone or with otherorganohalosilanes or oyclopolysiloxanes. Standard equilibratingcatalysts such as potassiumhydroxide, ferric chloride hexahydnate,phenylphosphorylchloride, etc. can be employed. Ternper-atures in therange of 100 C. utilized during the cohydrolysis and intercondensationre,- action.

In order that those skilled the maybe better able to understand thepractice of the present invention, the following examples, are given byway of illustration and not by way of limitation. All parts are byweight.

EXAMPLE 1 g V There was added to a reaction'vessel equipped with areflux condenser, thermometer and dropping funnel, a mixture of about.015 part of platinum in a finely divided norm on carbon 'and- 26 partsof 1,1,1-trifluoroethcxyethylene that contained an antioxidant. .Themixture was heated to 40 C. and 37 parts methylhy drogen dichlorosilanewas slowly added to the. heated mixture over a period or one hour. Thereaction temperature rose from 42 'C. to 84 C. during the addition. Themixture was refluxed for tvvo additional hours. The crude productwasthen'distilled at 86? C. (50 nun), and there was recovered 48 partsof a product having the formula:

Thisproduct had a refractive index n 1.3952 and contained 29.41 percentchlorine as compared with the theoretical value of 29.42;

I EXAMPLE 2 The procedure of Example 1 was repeated except that 34 partsof trichlorosilane was added over a period of 1 hour toa mixture of 20parts-of 1,1,1-trifluorethoxyethylene and .015 part of'platinum catalyston carbon.

Durin'gthe addition the temperature rose from36 to 40? C. and the refluxwas continued ttor an'additional 8 hours. The final product (3.5 parts)was found to have a boiling oint of 83-85" C. at 44 millimeters and hadthe formula: V I 4 cr cn -o 'on on mtol ExAM-PiLEs p A mixture 0 5-20am;of amuseme ts, 0.5: part of trimethylchlorosilane, 50 parts or tolueneand trifiuoroethoxyethylsilylrnethyldi j vessel; Water was added to themixture while stirring at a temperature of 20 C. The resulting mixturewas halt hour FM 20 C. aridfthen heated at 40 C. tor 1 /2 hours. Thecrude product was separated and stripped at "138 ing a viscosity of 5centistokes at 25 C., and having the average formula:

(C s)1.1s (C F3CHZOCHZOHZ) ass-$0 5 EXAMPLE 4 There was added to avessel equipped with a stirrer, reflux condenser and thermometer, amixture of 12 parts of l,3,5,7-tetramethyl 1,3,5,7tetrahydrocyclotetrasiloxane and 25 parts of.1,1,ltrifluoroethoxyethylene. In addition, 0.7 part of 2% platinum on carboncatalyst was added to the mixture. The resulting mixture began to: re-

' flux at 40 C. and reflux was continued for six hours to a 15temperature of 50 to 180 C. can be A i the final product was C. Therewas then added 0.01 part of chloroplatinic acid to further catalyze thereaction. The temperature rose to 98 C. and then the temperature felloff rapidly. The mixture was distilled under reduced pressure (5 mm.)and 20 parts of a cyclic product having the formula:

, lo LC sC 20 (xiv-( 3112.14

wasrecovered. This product had a refractive index r1 1.3 840. I

Q0115 V S iGlz 7 oF3 oH2o-oH2oH2 This product contained 23.34percentchlorine as compared with the theoretical value of 23.47.

- EXAMPLE 6 A mixture of 6.8 parts ofthe, fiuoroethoxyethyl sub- -aguru.

stituted cyclotetrasiloxane' of Example 4, and 0.015 part of potassiumhydroxide was heated for, 30 minutes in a reaction vessel atatemperature of 150 C. There was then added 6 parts of.octamethylcyclotetrasiloxane, and the resulting mixture was heated for30 minutes at 165 C. An additionalj12 parts. ofoctamethylcyclotetrasiloxane was added to the reaction mixture and themass was stirred for another hour. Another increment of 24 parts ofoctamethylcyclotetrasiloxane was added, and after. another hour, ofstirring, a final increment of 35 parts was added. The mass polymerizedshortly thereafter to A v This gum contained 5 mol percent of1,1,1-trifluoroethoxyethyl radicals based on the total numberof organicradicals in the polymer. Amixture of 100 parts of'th'e above gum,referred [to inthe table below asthe fiuoroalkyl polymer, 40 ,parts ofsilica filler and, 2 partsofbenzoyl peroxide was blended in adoughmixer. The mixture was, milled and I test sampleswerecut from asheet. that was press-cured for lO minutes at C." nd post -cured for 16hours at C. 5 =74" Control strips were made by a, similar procedure froma'silica reinforceddimethylpolysiloxane gum formulation. The curedstrips contain ingthe fluoroalkyl polymer and the control were testedfor swell resistance as follows:

C. pot temperature.

'lhere was dljtained 25 parts of 9. nuts, {r15 5 013923 hav- .75'

: The test strips wereimmersed a mixture of 70 volumes isooctane and30volumes toluene for 3 hours at room temperature. The table below-showsthe relative percent increase in volume in the strips as compared totheir original volume.

The above results show that organopolysiloxane elastomer compositionsthat contain 1,1,1-trifluoroethoxyethyl a where R is a member selectedfrom the class consisting radicals attached to silicon throughcarbon-silicon linkages have improved swell resistance compared to acontrol that is free of trifluoroethoxyethyl radicals.

The trifluoroalkoxyalkyl substituted organosilicon compounds of thepresent invention illustrated by Formulae l and 2 are valuable asintermediates for the production of a wide variety of useful materials.The presence of fluorine radicals in organopolysiloxane elastomers andgreases as shown in Formula 5 has been found to impart to thesematerials improved resistance to the effects of solvents, particularlyorganic solvents. Trifiuoroalkoxyalkyl substituted organopolysiloxaneresins have been found to be valuable in electrical insulating,laminating and protective coating applications. Because of their highdegree 'of ionic functionality, these substituted organopolysiloxanesare also eminently suitable as surfactants. Additionally thecompositions of the present invention can be employed in the treatmentof paper, and metal castings as release agents, sealants, adhesives,lubricants, in the treatment of masonry, ceramics, etc.

While the 1 foregoing examples have of necessity described only a few ofthe very many trifluoroalkoxyalkyl organosilicon compositions of thepresent invention, it should be understood that the present invention isdirected to a much broader class of compositions as illustrated byFormulae 1 and 2, in addition to the organopolysiloxanes derivedtherefrom. 1

What I claim as new and desire to secure by Letters Patent of the UnitedStates is:

1. Organopolysiloxanes having the formula:

1%): [Om-o(R)00HR+0(R)1];S10 2 Where R is a member selected from theclass consisting of hydrogen and lower \alkyl groups, R" is a memberselected from the class consisting 01f monovalent hydrocarbon radicals,halogenated monovalent hydrocarbon of hydrogen and lower alkyl groups, Ris a member selected from the class consisting of monovalent hydrocarbonradicals and halogenated monovalent hydrocarbon radicals, a is aninteger equal to from O to 2, inclusive, and X is hallo.

3. Oyclop-olysiloxanes having the formula:

L a t 1. Lil

where R is a member selected from the class consisting of a ReferencesCited in the file of this patent UNITED STATES PATENTS 2,465,188 Barryetal. Mar. 22, 1949 2,651,651 Simons Sept. 8, 1953 2,682,512 Agre June29, 1954 2,800,494 Haluska July 23, 1957 2,823,218 Sper et a1. Feb. 11,1958 2,892,859 McBee et a1. June 30, 1959 2,894,969 Pierce July 14, 19592,979,519 Pierce et al. Apr. 11, 1961 2,983,711 Gordon May 9;, 19612,983,746 Smith et ial.. May 9, 1961 3,006,878 Talcott Oct. 31, 19613,038,000 Schmidt June 5, 1962 OTHER REFERENCES Eabom: Orga-nosiliconCompounds, Academic Press, Inc, 1960, pages 51-64 relied on.

1. ORGANOPOLYSILOXANES HAVING THE FORMULA:
 2. ORGANOSILANES HAVING THEFORMULA: